EP0723396A1 - Compositions et procedes inhibant la formation de chloramines et de trihalomethanes en milieu aqueux - Google Patents

Compositions et procedes inhibant la formation de chloramines et de trihalomethanes en milieu aqueux

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Publication number
EP0723396A1
EP0723396A1 EP94912187A EP94912187A EP0723396A1 EP 0723396 A1 EP0723396 A1 EP 0723396A1 EP 94912187 A EP94912187 A EP 94912187A EP 94912187 A EP94912187 A EP 94912187A EP 0723396 A1 EP0723396 A1 EP 0723396A1
Authority
EP
European Patent Office
Prior art keywords
glycoluril
chlorine
ppm
water
source composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP94912187A
Other languages
German (de)
English (en)
Other versions
EP0723396A4 (fr
Inventor
Ronald Lee Jones
Henry Daniel Caughman
Susan M. Shelor
Ellwood Leroy Lines, Jr.
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bio Lab Inc
Original Assignee
Bio Lab Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bio Lab Inc filed Critical Bio Lab Inc
Publication of EP0723396A1 publication Critical patent/EP0723396A1/fr
Publication of EP0723396A4 publication Critical patent/EP0723396A4/fr
Withdrawn legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/76Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/42Nature of the water, waste water, sewage or sludge to be treated from bathing facilities, e.g. swimming pools
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00Technologies for wastewater treatment
    • Y02W10/30Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37Wastewater or sewage treatment systems using renewable energies using solar energy

Definitions

  • the present invention relates generally to disinfectant systems for swimming pools, spa water, cooling tower water and other aqueous media. More particularly, the invention relates to systems utilizing chlorine as a disinfectant, and to compositions and methods for inhibiting the production of chloramines and trihalomethanes in such systems.
  • Chlorine in various forms, is the most widely used chemical for this purpose, being both economical and highly effective for bacteria and algae control.
  • the use of chlorine presents certain problems however, including the need to stabilize the chlorine to prevent its depletion over an extended period of time.
  • trihalomethanes such as chloroform
  • these compounds not only cause eye and skin irritations, at certain concentrations they are toxic by inhalation. Even at concentrations insufficient to be toxic, trihalomethanes have distinctive odors which are objectionable for certain applications.
  • the present invention addresses that need.
  • FIG. 1 shows chloramine volatility over time in the presence of ammonia, with and without glycoluril.
  • FIG. 2 shows chloramine volatility over time when 1.2 ppm glycoluril is added to a chlorine-containing media.
  • FIG. 3 shows chloramine volatility over time when glycoluril is added at a 5.0 ppm concentration level.
  • FIG. 4 is another example of chloramine volatility over time when glycoluril is added at a 5.0 ppm concentration level.
  • chlorine as a disinfectant for swimming pool water, cooling tower water and other aqueous media has been well known for many years.
  • chlorine compounds are continuously or periodically added to the water to maintain a microbicidal concentration of chlorine. Without periodic addition, the effective chlorine concentration in the water will decrease due to dissipation, reaction, conversion into unusable forms, etc.
  • the useful life of added chlorine has been undesirably short, and there has remained an unsatisfied need for extending the effective life of added chlorine compounds.
  • the present invention provides compositions, systems and methods for extending the useful life of chlorine provided to aqueous media for disinfecting purposes, while also reducing the production of trihalomethanes and chloramines.
  • the present invention utilizes the activity of glycoluril as a stabilizer for chlorine in an aqueous environment.
  • Addition of the glycoluril and chlorine compositions may be at the same or different times, continuous or periodic, and by any of a variety of addition methods.
  • the presence of the glycoluril at a stabilizing concentration suited to the chlorine concentration will result in an extended effective life for the chlorine in a state suitable for microbicidal activity.
  • the half-life for trichloro-s-triazinetrione (TCCA) in a given system is about 6-7 hours, whereas use of glycoluril in the system extends the half-life to about 20-25 hours.
  • the present invention utilizes a glycoluril-source composition that provides glycoluril to stabilize and prolong the useful life of the chlorine while inhibiting the formation of chloramines and trihalomethanes and the odors which may be caused thereby.
  • Glycoluril-source compositions useful with the present invention include any composition which will contribute a glycoluril compound compatible with and useful for stabilizing the chlorine, and suitable for the aqueous media being treated. Substitution on the glycoluril is not critical, provided that the substituents do not interfere with the utility of the glycoluril in the manner described herein.
  • glycol encompasses a compound which includes the basic formula:
  • glycoluril in which a is either 0 or I.
  • useful glycoluril-source compositions include the chloro, alkyl and phenyl substituted glycolurils.
  • glycoluril thus includes compounds of the foregoing basic structure (I), as well as compounds including substituents such as alkyl, phenyl and chloro groups at available bonding sites. Bromo-substituted glycolurils may also be useful in certain applications, although the presence of the bromine substituent may interfere in some systems with the utility of the glycoluril as a chlorine stabilizer.
  • glycoluril-source compositions include glycolurils having the following structure:
  • R and R are independently selected from the group consisting of hydrogen, lower alkyl radicals of from 1 to 4 carbon atoms, and phenyl; each X is either hydrogen, chlorine or bromine; and a is either 0 or 1. It is preferred that R and R, be either hydrogen or methyl, as alkyl radicals with longer carbon lengths render the glycolurils less soluble in water.
  • the chlorine concentration in the aqueous media may be obtained from any suitable source which provides hypochlorous acid (HOC1) to the water.
  • Chlorine-source compositions may include both inorganic and organic materials. Useful inorganic materials include molecular chlorine, lithium hypochlorite (LiOCl) . Calcium hypochlorite (Ca(OCl) 2 ) , sodium hypochlorite (NaOCl) and hypochlorous acid (HOC1).
  • Organic sources may include, for example, bromochlorodimethylhydantoin (BCDMH) , dichlorodi ethylhydantoin (DCDMH) or compositions based on cyanuric acid, such as sodium or potassium dichloro-s-triazinetrione or trichloro-s-triazinetrione (TCCA) .
  • BCDMH bromochlorodimethylhydantoin
  • DCDMH dichlorodi ethylhydantoin
  • compositions based on cyanuric acid such as sodium or potassium dichloro-s-triazinetrione or trichloro-s-triazinetrione (TCCA) .
  • BCDMH bromochlorodimethylhydantoin
  • DCDMH dichlorodi ethylhydantoin
  • compositions based on cyanuric acid such as sodium or potassium dichloro-s-triazinetrione
  • the chlorine source is not critical to the present invention, provided that the source is compatible with the aqueous media system being treated and is stabilized by the glycoluril compound which is utilized.
  • a wide variety of aqueous media may be treated by the present invention. In general, any aqueous media which is effectively treated with chlorine, and which is compatible with the described chemicals, can be treated.
  • Typical systems for which the present invention is useful include swimming pools, spas, hot tubs and health related baths, decorative fountains, recirculating water cooling systems, dehumidifier systems, ponds, reservoirs and waste water systems.
  • the concentrations of glycoluril and chlorine will vary depending on the aqueous media being treated.
  • An advantage of the present invention is that the level of glycoluril can be readily matched to the desired chlorine concentration effective for the given aqueous system.
  • the selected glycoluril level will facilitate maintaining the desired microbicidal level of the chlorine in the water.
  • the appropriate concentrations of the chlorine, and therefore of the glycoluril will also differ based upon the conditions attendant to the aqueous media. For example, effective levels may differ based upon such factors as the extent and nature of activity needed, the presence of other treatment chemicals, and conditions of use such as temperature, amount of sunlight, pH and the like. Generally, any factors which affect the stability of the chlorine will have an impact on the desired glycoluril levels.
  • the present invention contemplates that the desired level of chlorine and of glycoluril can be readily determined by one of ordinary skill in the art without undue experimentation, and specific concentrations therefore are not specified herein for each variety of treatable aqueous systems.
  • the level of glycoluril in the water is that which provides an effective concentration of glycoluril to usefully stabilize the chlorine present in the system while inhibiting the formation of chloramines, trihalomethanes and odors.
  • Typical concentrations of glycoluril effective as described will range from about 0.1 to about 40.0 ppm. More preferably, the glycoluril is present at a concentration of from about 5.0 to about 20.0 ppm, although concentrations of up to about 100 ppm may be used.
  • glycoluril As high as 100 ppm is the initial treatment of a pool. In this way the level of glycoluril will remain at an effective level for a prolonged period of time. In addition, such high levels of glycoluril may be used with particularly high levels of chlorine.
  • the concentration of the chlorine in the water is that which provides an effective level of chlorine for the degree of microbicidal activity desired for the given aqueous media.
  • the term total available chlorine is used herein to include both free chlorine and combined chlorine.
  • a suitable concentration of total available chlorine will be in excess of about 1.0 ppm, and preferably will range from about 1.0 to about 5.0 ppm in the water. This is true, for example, in the case of swimming pool water.
  • the desired total available chlorine level in cooling tower water may differ, ranging from about 1.0 to about 10.0 ppm total available chlorine.
  • One aspect of the present invention advantageously uses two separate compositions, one primarily providing the chlorine and the other primarily providing the glycoluril.
  • the overall effect is that the glycoluril is maintained at a level which both prolongs the useful life of the chlorine in the system and reduces the formation of chloramines, trihalomethanes and odors.
  • certain forms of glycoluril-source compositions may include chlorine which will be contributed to the water, such forms of glycoluril are contemplated in the present invention as primarily stabilizing compositions. Indeed, the amount of chlorine which can be added to the water through a chlorinated form of glycoluril is typically either insufficient, or would require the use of amounts of chlorinated glycoluril which are otherwise undesirable.
  • the glycoluril and chlorine compositions may be administered to the aqueous media in any manner effective to provide the desired concentrations of each compound.
  • the glycoluril and chlorine may be added to the water either together or separately, and either periodically or continuously.
  • the methods of application may vary with the aqueous systems being treated, and the conditions of use pertinent thereto. In general, however, the methods are restricted only by the need to maintain effective levels of the glycoluril and chlorine as described, and may be any suited to the physical forms and particular compounds employed.
  • Existing disinfectant systems using chlorine contemplate various methods for maintaining a desired level of the chlorine in an aqueous system.
  • the present invention is advantageous in that it may be readily adapted for use with a wide variety of such existing water treatment systems.
  • compositions useful in the present invention may be readily prepared in forms and concentrations convenient for broadcast application.
  • the erosion method compositions are fabricated into a solid-form material which is contacted with the water in a manner to effect a relatively slow erosion of the solid material, thus gradually releasing the composition into the water.
  • the composition to be added is formed or compressed into solid forms, such as tablets, sticks, pucks and other shapes, typically by a hydraulic or mechanical press.
  • the solid-form materials may include inert fillers, such as sodium chloride or boric acid, that assist in the tabletting process.
  • the solid material may also contain other ingredients such as tabletting aids, e.g., mold release agents, binders, corrosion inhibitors, scale inhibitors and other components known to those skilled in the art.
  • Erosion methods are commonly employed in the prior art for introducing chlorine-source compositions into swimming pools, for example.
  • the chlorine composition in solid form, is placed into a release device through which water is circulated to erode the solid material.
  • the tablet, stick or puck can be placed into a skimmer basket, in-line or off-line feeders, or a floating release device.
  • erosion may also be used for the glycoluril, it has been found that at least certain forms and types of glycoluril are not well suited to introduction by continuous erosion methods, because for these forms the erosion method provides insufficient levels of glycoluril in the water.
  • the glycoluril-source and chlorine-source compositions may be provided either as two separate materials or as a physically combined product, depending on the form and intended manner of addition of the products.
  • the provision of separate materials is preferred since the preparation of the compositions is thereby made simpler.
  • the methods and compounds for adding the chlorine and the glycoluril are more flexible, for example permitting the use of liquid chlorine with a granular glycoluril composition, or permitting the continuous erosion addition of the chlorine and a periodic broadcasting of the glycoluril composition.
  • the separate addition further enables the user to independently control the concentrations of the two compounds, which will be particularly useful if the water conditions result in a disparate depletion of one compound compared to the other.
  • Additive glycoluril-source compositions can be readily formulated to provide the desired levels of glycoluril in water upon addition of prescribed amounts of material at indicated time intervals.
  • granular forms of the compositions may be readily prepared which give desired concentrations of glycoluril when added to the water at intervals ranging from daily to every week or two.
  • the frequency of addition will depend on the conditions to which the water is subjected, and also on the amount, concentration and type of glycoluril-source composition being added.
  • the foregoing method may be enhanced by using as the chlorine source a mixture of a chlorine compound and a glycoluril compound in a physical combination which facilitates sustained release of the chlorine compound into the water.
  • a tablet or stick form of chlorine-source material may be formulated which also includes a percentage of glycoluril.
  • the glycoluril is formulated with the chlorine-source compound in the solid tablet or stick because it has been found that this will slow the erosion rate for the solid material. This in turn extends the life of the solid material and reduces the frequency with which the tablets or sticks need to be replaced. Consequently, the chlorine is added to the aqueous system at a controlled and uniform rate over a longer period of time.
  • the tablet in this method will also contribute a certain amount of glycoluril to the water, but the desired level of glycoluril may not be primarily obtained from this source. Instead, a glycoluril-source compound is also otherwise added into the water, such as by periodic broadcasting, to bring up and maintain the level of glycoluril in the water as desired.
  • the solid form tablets or sticks are formulated to include both chlorine and glycoluril source compounds.
  • the chlorine compound is preferably selected from the group consisting of calcium hypochlorite, lithium hypochlorite, sodium dichloro-s-triazinetrione, potassium dichloro-s-triazinetrione, and trichloro-s-triazinetrione, and is present in an amount of from about 50.0% to about 99.99% by weight.
  • the glycoluril-source composition is preferably selected from the group consisting of glycoluril, alkyl-substituted glycoluril, phenyl-substituted glycoluril, and chloro-substituted glycoluril, and is present in an amount of from about 0.01% to about 50.0% by weight.
  • solid-form chlorine material comprises approximately 50-99.99% by weight of trichloro-s-triazinetrione and
  • the solid-form material includes approximately 50-99.9% by weight of trichloro-s-triazinetrione, 0.01-50% by weight of glycoluril and 0-20% by weight of an alkali bromide salt.
  • a preferred composition is 80-98% trichloro-s-triazinetrione (TCCA) and 2-20% glycoluril, or 70-90% trichloro-s-triazinetrione (TCCA), 5-10% sodium or potassium bromide salt, and 5-20% glycoluril.
  • Another preferred mixture is 75-90% trichioro-s-triazinetrione, 5-10% potassium bromide and 5-20% glycoluril.
  • the preferred glycolurils are unsubstituted glycoluril (I) and the chloroglycolurils, such as dichloroglycoluril and tetrachloroglycoluril.
  • glycoluril is preferred.
  • the present invention is well suited to use in the treatment of swimming pool water. Current systems provide for the addition of chlorine to maintain certain accepted levels, typically 1 to 5 ppm of total available chlorine in the water.
  • the present invention may be directly adapted for use in the variety of prior art systems which utilize chlorine as a disinfectant by maintaining in such systems the indicated levels of glycoluril effective to both stabilize the chlorine and reduce the formation of chloramines, trihalomethanes and odors.
  • the glycoluril also may be used with various other treatment chemicals typically used in such systems, such as algicides, clarifiers and the like.
  • compositions may be readily formulated so as to be specifically adapted for use in swimming pools or other water systems.
  • swimming pool chemicals for example, are typically constituted to require the addition of convenient, prescribed amounts on a periodic basis, usually weekly.
  • the chemicals utilized in the present invention can be formulated on this basis. More preferably, one aspect of the present invention prolongs the useful life of the chlorine to the point that the frequency of addition of chemicals may be extended beyond the usual weekly basis, perhaps to once every two weeks or longer.
  • the process of the present invention would proceed as follows. About every week the user employs a prescribed amount of solid-form, chlorine-source tablets or sticks in an erosion device.
  • the solid-form material includes the chlorine-source composition and glycoluril, for example about 95% TCCA and about 5% glycoluril.
  • This formulation has a slowed erosion rate compared to prior art chlorine products, and therefore will last up to two weeks or more.
  • the stabilizing of the chlorine effected by the glycoluril matches well with the extended erosion life of these alternate tablets or sticks.
  • shock may be conveniently performed, for example every two weeks, by adding a conventional material, such as sodium dichlorocyanurate, at the same time as the addition of the glycoluril.
  • a full pool treatment system would then only require the addition of algicide, such as a quaternary ammonium compound, at the same two week interval, thus providing the user with a convenient system and method for the treatment of swimming pool water.
  • the ratio of glycoluril to total available chlorine can be selected to optimize the duration and microbicidal efficacy of the chlorine.
  • the amount of glycoluril in the water is preferably limited to an extent appropriate to result in sufficient hydrolyzing of the chlorine. It is possible that the presence of too much glycoluril in comparison to the amount of total available chlorine will affect the amount of chlorine in solution, and therefore the microbicidal activity.
  • the glycoluril can be present in such high amounts relative to the chlorine that the chlorine is made so stable as to reduce its microbicidal activity. For example, a standard hypochlorite solution will effectively kill 10 bacteria in about 30 seconds.
  • a ratio of glycoluril to total available chlorine of about 5:1 will result in a kill of about half of the bacteria in about two minutes, and higher ratios will further delay the kill time. Therefore, although water systems having higher ratios of glycoluril to total available chlorine will still have microbicidal efficacy, the performance will be diminished. It has been found that preferred ratios of total available chlorine to glycoluril are from about 10:1 to about 1:10, more preferably about 5:1 to about 1:5. While increased stability of chlorine is normally associated with decreased microbicidal activity, the present invention provides increased stability and desired microbicidal activity.
  • the present invention is useful in a wide variety of applications. A person skilled in the art can readily determine the suitability of given chlorine-source and glycoluril-source compositions for a particular aqueous system.
  • the present invention may also be used in conjunction with a variety of other chemicals such as algicides, fungicides, clarifiers, pH adjusters, sequesterants and the like, and may be used with other chlorine stabilizers such as cyanuric acid, oxazolidinone, imidazolidinone, dimethylhydantoin, succinimide, toluenesulfonamide, sulfonamidobenzoic acid, melamine, dioxohexahydrotriazine, piperazinedione, and azodicarbonamidine.
  • the present invention has also been found to provide several ancillary benefits to the aqueous systems.
  • glycoluril in the amounts indicated reduces the offensive chloramine odor associated with certain chlorinating systems. such as those using TCCA.
  • the development of trihalomethanes is diminished in the presence of the glycoluril.
  • objectionable compounds and odors in aqueous systems are inhibited by maintaining concentrations of 1-100 ppm cyanuric acid (1-40 ppm preferred), 1-100 ppm glycoluril (preferred 5-20) and 1-5 ppm available chlorine in the water.
  • the chlorine is provided by a compressed form of trichloro-s-triazinetrione which also contains up to about 50% glycoluril.
  • This compressed source of available chlorine has the unique property of dissolving appreciably slower than compressed 100% trichloro-s-triazinetrione.
  • the glycoluril in the water greatly stabilizes the chlorine in the system.
  • compositions and methods of the present invention permit an easier swimming pool sanitation program when compared to traditional pool chlorine treatments.
  • fresh compressed clilorine additions to a skimmer or an erosion control device need to be made only infrequently, making it possible to be gone for a minimum of 2 weeks without getting algae, cloudy water or other water problems.
  • a person may simply add the compressed clilorine (with glycoluril) to the skimmer or chlorinator, and set the time clock to operate the pump and filter for the prescribed hours each day.
  • the treatment of the present invention anticipates a superchlorination or other "shock" treatment to remove inorganic and organic materials. With the present invention, this may be accomplished with peroxymonopersulfate in lieu of clilorine. Glycoluril at the preferred levels improves the odor of swimming pool water due to reduced formation of inorganic chloramines, organic chloramines and other odorous organic chlorides. Pools treated as described herein also have less tendency to have acid pH drift, further inhibiting the formation of odorous and irritating chloramines.
  • the present invention aids in reducing pool odors regardless of whether the clilorine used is inorganic hypochlorite (calcium, lithium, sodium or potassium) or organic (trichloro-s-triazinetrione or sodium dichloro-s-triazinetrione) .
  • Example 1 This Example illustrates a method for treatment of water systems in accordance with the present invention. This experiment was conducted to demonstrate the rate of loss of chlorine from solutions containing cyanuric acid, glycoluril and mixtures of the two. This experiment was conducted under controlled conditions designed to simulate conditions expected while operating a pool under full sunlight.
  • the chlorine source for this study was trichloro-s-triazinetrione (TCCA) .
  • TCCA trichloro-s-triazinetrione
  • the objective of this study was to determine the rate of loss of total available chlorine (TC1 Rad) from water systems containing cyanuric acid, glycoluril and mixtures of the two, when exposed to ultraviolet light in the wavelength region of 295-340 nm.
  • the chlorine half-life was determined by plotting % remaining total available chlorine (TC1 2 ) vs. time (hours) .
  • TC1 2 % remaining total available chlorine
  • time hour
  • Example 3 This Example examines the potential for glycoluril to build up through normal swimming pool usage.
  • a 20,000 gallon vinyl in-ground pool was filled with water and balanced to the following specifications: Calcium Hardness: 175 ppm
  • the pool was maintained at 1 to 3 ppm total available chlorine using compressed, one-half pound TCCA sticks, and was shocked biweekly using lithium hypochlorite to bring the total available chlorine level to 8 ppm.
  • glycoluril level ranged from 1 to 5 ppm. A sum of 1125 grams of glycoluril was added to the pool during the test period. At the end of the test period less than 1 ppm of glycoluril was measured in the water.
  • Example 4 This Example illustrates the ability of glycoluril to reduce the volatility of chlorine and inorganic chloramines from aqueous systems, thereby reducing the offensive odors caused by the compounds. The results indicate that the glycoluril appears to effectively retard the loss of free chlorine and inorganic chloramines from aqueous systems.
  • Chlorine was dosed into Erlenmeyer flasks containing one liter of demand free water (18 megohm resistance) at a concentration of 2 ppm. Ammonium chloride concentration was 2 ppm. Glycoluril was added to give a final concentration of 1.2 or 5 ppm. Flask 1 contained chlorine and 5 ppm glycoluril, flask 2 contained chlorine and the ammonium salt, flask 3 contained chlorine, the ammonium salt and 1.2 ppm glycoluril, and flask 4 contained chlorine, the ammonium salt and 5 ppm glycoluril. In flasks 3 and 4, the ammonium chloride was added after the addition of the chlorine and glycoluril. The results are shown in Table V and in FIG. 1.
  • FIG. 1 shows the results of the experiment with concentrates of glycoluril of 1.2 and 5.0 ppm. It is apparent that the addition of glycoluril to chlorine in Flask #1 was able to dramatically slow the volatilization of chlorine. In the presence of ammonia, 1.2 ppm glycoluril reduced the chloramine volatilization slightly. At 5 ppm glycoluril in the presence of ammonia, the chloramine volatilization was reduced to a greater extent.
  • Example 6 The following Example illustrates the effectiveness of glycoluril to inhibit the formation of trihalomethanes (THM) from humic acid.
  • Test solutions were prepared in new 120 ml vaccine bottles which were washed with cliromic acid cleaning solution, rinsed in hot tap water, and then in distilled water before use.
  • the following stock solutions were prepared for use in these tests: a 200 ppm solution of available chlorine from commercial bleach, a 0.1% humic acid solution (Humic acid (HA), sodium salt; Aldrich Chemical Co., Inc., CAS # 1415-93-6), a 0.04% glycoluril solution, and a 0.1% s-triazinetrione (CYA) solution.
  • Thirteen solutions were prepared as outlined in Table VI.
  • Each bottle was 3/4 filled with boiled distilled water, and the stock solutions were then added thereto.
  • Eacli bottle was then filled to the top with boiled distilled water, covered with a TEFLON® cap, and sealed with a metal vaccine crimp cap.
  • the bottles were held at room temperature overnight and the next day were analyzed for the presence of trihalomethanes.
  • the solutions were analyzed for chloroform, bromoform, bromodichloromethane and dibromochloromethane, and the results are shown in Tables VII and VIII.
  • Solutions 1-4 represented varying concentrations of glycoluril in combination with 15 ppm humic acid and chlorine.
  • the results indicate that 5 and 10 ppm glycoluril almost completely prevented chloroform formation, while 25 ppm only inhibited formation by 55.5%, and 50 ppm glycoluril only resulted in 25.5% reduction over the positive control. It is therefore shown that low levels of glycoluril (5 and 10 PP ) prevent chloroform formation from humic acid almost completely, while higher concentrations inhibit THM formation but to a lesser extent.
  • the impurity was too low to form an appreciable amount of chloroform, while at the higher concentrations there was sufficient impurities to appreciably affect the test.
  • the tests do demonstrate the effectiveness of glycoluril to prevent or inhibit the formation of THMs.
  • Solutions 5-8 represent varying levels of glycoluril with 50 ppm CYA. This treatment group gave good reduction over the positive control, and the results were consistent with varying concentrations of glycoluril. There was some slight chloroform inhibition at 5 ppm glycoluril and greater inhibition at 10, 25 and 50 ppm glycoluril in combination with the CYA. Maximum inhibition was reached at 25 pprn, with no improvement at 50 ppm. Thus, the optimum glycoluril range may be in the range of 10-40 ppm.
  • Example 7 The following Example demonstrates the prevention of offensive odors due to the creation of simple inorganic chloramines. Two beakers were each filled with 2000 ml distilled water and the pH was adjusted to 7.2. In the first beaker 50 ppm CYA was added along with 10 ppm TC1_ from a TCCA stock solution. The solution was allowed to mix for 10 minutes.
  • Example 8 The following Example demonstrates the effect of glycoluril and related compounds on the formation of chloramines and chloramine odors from combinations of available chlorine and nitrogen from ammonium chloride.
  • Hard water having 400 ppm calcium and with a pH of 4.0 was used as the diluent in the following tests.
  • Compounds tested included glycoluril (G), dimethylhydantoin (DMH) and 4,4-dimethyl-2-oxazolidinone (DMO) and s-triazinetrione (CYA) .
  • G, DMH, DMO and CYA are commercially available.
  • a 0.02% available chlorine solution (200 ppm) was prepared by dissolving 0.61 grams of lithium hypochlorite in 1 liter of distilled water. The solution was titrated iodo etrically before use in the test. The solution titrated at 0.18%, so 2.2 nil was used in the tests to obtain 20 ppm available chlorine in each test solution. Fresh 0.04% stock solutions of G, DMO and DMH were prepared in distilled water for these tests.
  • Test solutions were prepared in PYREX® test tubes and were covered with stainless steel caps between preparation and use in the odor tests. Solutions were tested for odor within three hours of preparation. Solutions were kept at ambient room temperature during preparation and testing.
  • test solutions were set up for each test compound as indicated in the following Table.
  • the ratio of ammonium nitrogen to available chlorine was approximately 1:10, an optimum ratio for the formation of chloramines from ammonium.
  • the odor score for each test solution was determined by averaging the nine individual panelist scores. Thus, the lowest possible score (no odor) would be 0 and the highest odor score possible would be 4.0 (maximum odor). Table X
  • CYA + G contained 50 ppm CYA and the amount of glycoluril sho in column 2.
  • Glycoluril reduced odor scores by approximately 50% at 5 and 10 ppm levels and gave odor scores approximating chlorine with no ammonium nitrogen added at 25 and 50 ppm levels. Thus, at 25 and 50 ppm levels chloramine odor formation was apparently eliminated by the compound.
  • CYA was marginally effective at 5 and 10 ppm and was effective at 25 and 50 ppm.
  • the high odor reading for tube 8, the chlorine control for CYA, is an apparent aberration, possibly due to an error in preparation or a dirty piece of glassware.
  • Example 2 is a further demonstration of the effect of glycoluril and related compounds on the formation of chloramines and chloramine odors from combinations of available chlorine and nitrogen from ammonium chloride.
  • Acid cleaned glassware was used in this study. Hard water at 400 ppm calcium and a pH of 4.0 was used as the diluent.
  • Compounds tested included glycoluril (G) , dimethylhydantoin (DMH), 3,3,5,5-tetramethyl-2-imidazolidinone (TMI), 4,4-dimethyl-2-oxazolidinone and s-triazinetrione (CYA). All of the compounds tested, except TMI, are commercially available.
  • Tests were performed in PYREX* test tubes. The concentrations of solutions were as outlined in Table XI. The ratio of nitrogen to chlorine in these tests was 1:10. Nitrogen concentrations were 2 ppm and available chlorine concentrations were 20 ppm.
  • the solutions were ranked for odor by a panel of 13 people.
  • the odor score for each test solution was determined by averaging the 13 panelists' scores.
  • Example 10 The following Example demonstrates the effect of glycoluril on chlorophenol formation in mixtures of phenol and chlorine.
  • the effect of glycoluril source compositions on the formation of chlorophenol odors is demonstrated herein. It is reported that chlorophenols have a threshold odor detection level of 1-3 ppb, whereas chlorine and chloramines have threshold odor detection levels of approximately 0.15-0.65 ppm. This difference in odor detection levels allows for dilutions of reaction mixtures to track the formation of chlorophenols. In this study it was assumed that the detection level was 3 ppb in order to provide an analytical tool.
  • Chlorine solutions of approximately 100 ppm available chlorine were prepared in distilled water from the following compositions: trichloro-s-triazinetrione (TCCA) and lithium hypochlorite (LiOCl) . Solutions containing the following in distilled water were prepared: Table XIII ube # ppm phenol ppm ppm avail. Cl2 ;
  • Lithium hypochlorite generated large quantities of chlorophenolic odorous compounds compared to trichloro-s-triazinetrione.
  • Glycoluril in the range of 5-10 ppm reduced the formation of chlorophenols by a factor of 40-60% in both the LI and TC treatment groups.
  • the reported detection levels for chlorophenols are 1-3 ppb.
  • the ppb chlorophenols were determined by taking the highest dilution of chemical mixture where a chlorophenol odor could be detected and multiplying this factor by 3 ppb (the minimum detectable level).
  • the results reported are an average of the observations for each of the six people used in the odor detection panel.
  • Glycoluril effectively reduced the formation of chlorophenols from phenol in the presence of 5 or 10 ppm available chlorine from an inorganic chlorine donor (lithium hypochlorite) and an organic, halamine (trichloro-s-triazinetrione) .
  • This Example shows the ability of glycoluril to inhibit the formation of odorous, chlorinous by-products in aqueous systems. It also illustrates the ability of glycoluril to reduce the formation of TOX (total organic halides) since chlorophenols are one example of such chemicals.
  • Example 11 This Example is a further demonstration of the effect of glycoluril and related compounds on odor formation from mixtures of phenol and chlorine. Chlorine solutions of 200 pprn available chlorine were prepared in distilled water from CHLOROX® bleach (sodium hypochlorite) . Solutions were prepared in acid cleaned tubes and were covered with parafilrn and held for two days at room temperature. Dilutions were then made in distilled water to obtain 1/25, 1/50, 1/100, 1/250, 1/500, 1/1000, 1/2500,
  • glycoluril to inhibit the volatilization of chlorine and chloramines was also tested. The results indicate that glycoluril effectively retards the loss of free chlorine from solutions. In addition, chloramine volatility is effectively reduced.
  • Example 4 To determine the effect of glycoluril upon the volatility of chlorine and chloramines, the airstripping apparatus of Example 4 was used. Air from an in-house air line initially passed through glass wool to trap solid particles and oil droplets. Next, the air went through a column filled with activated carbon to further clean the air stream. More glass wool was then Used to trap any carbon particles that may have escaped the column. Sequential filtering such as this is known to generate halogen demand free air. Demand free air was channeled into a sparging tank filled with demand free water. Air leaving the tank was accordingly saturated with water. This water-rich air was used to strip chlorine from the solutions used in the experiments. It was necessary to use water-saturated air to minimize evaporative losses in the flasks containing the halogen solutions.
  • FIG. 2 shows the results of an experiment when glycoluril was added at a concentration of 1.2 ppm.
  • glycoluril reduces the rate of chloramine volatility by about 29%.
  • FIG. 4 shows the results from a repetition of the previous experiment. Based on the slopes of the regressed data, the difference in chloramine volatility in the presence

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Abstract

Compositions et procédés de purification de milieux aqueux combinant une composition source de chlore et une composition source de glycoluril. Ces compositions sont ajoutées ensemble ou séparément, continûment ou périodiquement et selon l'un des nombreux procédés possibles. Le composé à base de glycoluril stabilise de chlore et prolonge sa vie utile de microbicide tout en réduisant en plus la formation de chloramines, de trihalométhanes et d'odeurs.
EP94912187A 1993-03-29 1994-03-08 Compositions et procedes inhibant la formation de chloramines et de trihalomethanes en milieu aqueux Withdrawn EP0723396A4 (fr)

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WO1993004987A1 (fr) * 1991-08-28 1993-03-18 Occidental Chemical Corporation Pastilles donneuses d'ions hypochlorite et d'ions bromure a dissolution lente dans l'eau
WO1993004582A1 (fr) * 1991-09-06 1993-03-18 Bio-Lab, Inc. Compositions et methodes de controle de l'accroissement des microbes en milieux aqueux

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US2789078A (en) * 1953-04-20 1957-04-16 Davies Young Soap Company Disinfecting and deodorizing compositions and method of using same
US2988471A (en) * 1959-01-02 1961-06-13 Fmc Corp Stabilization of active chlorine containing solutions
US3187004A (en) * 1961-05-01 1965-06-01 Diamond Alkali Co Halogenated alkyl and aryl substituted glycolurils
US3201311A (en) * 1962-01-19 1965-08-17 Armour Pharma Algicidal and sanitizing compositions
US3165521A (en) * 1962-06-21 1965-01-12 Diamond Alkali Co Halogenated glycolurils
US3342674A (en) * 1965-03-03 1967-09-19 Monsanto Co Sterilizing, sanitizing, and/or disinfecting shapes
US4780216A (en) * 1986-11-19 1988-10-25 Olin Corporation Calcium hypochlorite sanitizing compositions
US5015643A (en) * 1989-11-06 1991-05-14 Bio-Lab, Inc. Disinfectant for the treatment of water systems
US5000869A (en) * 1990-02-14 1991-03-19 Safe Aid Products, Inc. Novel polymer coated bleaching composition

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Publication number Priority date Publication date Assignee Title
WO1993004987A1 (fr) * 1991-08-28 1993-03-18 Occidental Chemical Corporation Pastilles donneuses d'ions hypochlorite et d'ions bromure a dissolution lente dans l'eau
WO1993004582A1 (fr) * 1991-09-06 1993-03-18 Bio-Lab, Inc. Compositions et methodes de controle de l'accroissement des microbes en milieux aqueux

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See also references of WO9422300A1 *

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